Polymer dopants for high electron conductivity in flexible energy devices

Abstract

A polymer having the structure N + Ar is a N-containing monocyclic or bicyclic aromatic ring having 1 or 2 N atoms, at least one of the N atoms is substituted with R a to have a positive charge and the ring is optionally substituted with R b , R a is H, thiophene, furan, pyridine, benzene, thiazole, C 1 -C 12 alkyl optionally substituted with one or more F atoms, or polyoxyethylene (—(CH 2 CH 2 O) n —H and R b is H, C 1 -C 12 alkyl, aralkyl, or C 1 -C 12 alkoxy. Ar is a phenyl or naphthalene ring, optionally substituted with R c or CO 2 Ph. Any of the phenyl or naphthalene rings is substituted with R c which is H, C 1 -C 12 alkyl, or C 1 -C 12 alkoxy, and R d is H or Me. X is halogen, bicarbonate (HCO 3 − ), carbonate, bisulfate (HSO 4 − ), bisulfite (HSO 3 −), methane sulfonate (MeSO 3 −). triethyl borohydride (Et 3 BH − ) or a C 1 -C 6 carboxylate. The ratio of x:y is from about 99:1 to about 1:99.

1 . A polymer having the structure 
       
         
           
           
               
               
           
         
         wherein N +  Ar is a N-containing monocyclic or bicyclic aromatic ring having 1 or 2 N atoms, at least one of the N atoms is substituted with R a  to have a positive charge and the ring is optionally substituted with R b , 
         wherein R a  is H, thiophene, furan, pyridine, benzene, thiazole, C 1 -C 12  alkyl optionally substituted with one or more F atoms, or polyoxyethylene (—(CH 2 CH 2 O) n —H and R b  is H, C 1 -C 12  alkyl, aralkyl, or C 1 -C 12  alkoxy, wherein any of the alkyl groups is optionally substituted with one or more F atoms; 
         Ar is a phenyl or naphthalene ring, optionally substituted with R c ′ or CO 2 Ph, wherein any of the phenyl or naphthalene rings is substituted with R c , wherein R c  is H, C 1 -C 12  alkyl optionally substituted with one or more F atoms, or C 1 -C 12  alkoxy optionally substituted with one or more F atoms; 
         R d  is H or Me; 
         X is halogen, bicarbonate (HCO 3   − ), carbonate, bisulfate (HSO 4   − ), bisulfite (HSO 3   − ), methane sulfonate (MeSO 3   − ), triethyl borohydride (Et 3 BH − ) or a C 1 -C 6  carboxylate; and 
       
       the ratio of x:y is from about 99:1 to about 1:99. 
     
     
         2 . The polymer of  claim 1 , wherein N +  Ar is selected from the group consisting of 
       
         
           
           
               
               
           
         
       
     
     
         3 . The polymer of  claim 1 , having the structure 
       
         
           
           
               
               
           
         
       
     
     
         4 . A polymer having the structure 
       
         
           
           
               
               
           
         
         wherein Ar is a phenyl or naphthalene ring, optionally substituted with R c ′ or CO 2 Ph, wherein any of the phenyl or naphthalene rings is substituted with R c , wherein R c  is H, C 1 -C 12  alkyl optionally substituted with one or more F atoms, or C 1 -C 12  alkoxy optionally substituted with one or more F atoms; 
         R b  is H, C 1 -C 12  alkyl, aralkyl, or C 1 -C 12  alkoxy, wherein any of the alkyl groups is optionally substituted with one or more F atoms; 
         R d  is H or Me; 
       
       R e  is 
       
         
           
           
               
               
           
         
          or 
         —CH 2 N + R 3  X −  or —CH 2 P + R 3  X − , 
         wherein R fa  is a chemical bond, thiophene, furan, pyridine, benzene, thiazole, or C 1 -C 6  alkyl optionally having one or more oxygens substituted for carbon and optionally having one or more F atoms on the alkyl chain, R f  is H, thiophene, furan, pyridine, benzene, thiazole, or C 1 -C 6  alkyl optionally having one or more oxygens substituted for carbon and optionally having one or more F atoms on the alkyl chain, R is C 1 -C 6  alkyl and X is halogen, bicarbonate (HCO 3   − ), carbonate, bisulfate (HSO 4   − ), bisulfite (HSO 3   − ), methane sulfonate (MeSO 3   − ), triethyl borohydride (Et 3 BH − ) or a C 1 -C 6  carboxylate; and 
         the ratio of x:y is from about 99:1 to about 1:99. 
       
     
     
         5 . The polymer of  claim 4 , wherein R is butyl. 
     
     
         6 . The polymer of  claim 4 , wherein R f  is H and R fa  is a bond. 
     
     
         7 . The polymer of  claim 1 , wherein Ar is a phenyl or naphthalene ring, optionally substituted with R c  and R d  is H. 
     
     
         8 . The polymer of  claim 1 , wherein the ratio of x:y is from about 95:1 to about 80:20. 
     
     
         9 . The polymer of  claim 1 , wherein the ratio of x:y is from about 95:5 to about 90:10. 
     
     
         10 . A polymer comprising the subunit 
       
         
           
           
               
               
           
         
       
       N +  Ar is a N-containing monocyclic or bicyclic aromatic ring having 1 or 2 N atoms, at least one of the N atoms is substituted with R a  to have a positive charge and the ring is optionally substituted with R b ,
 wherein R a  is H, thiophene, furan, pyridine, benzene, thiazole, C 1 -C 12  alkyl optionally substituted with one or more F atoms, or polyoxyethylene (—(CH 2 CH 2 O) n —H; 
 R b  is H, C 1 -C 12  alkyl, aralkyl, or C 1 -C 12  alkoxy, wherein any of the alkyl groups is optionally substituted with one or more F atoms; and 
 R c  is 
 
       
         
           
           
               
               
           
         
          or 
         —CH 2 N + R 3  X −  or —CH 2 P + R 3  X − , 
         wherein R fa  is a chemical bond, thiophene, furan, pyridine, benzene, thiazole, or C 1 -C 6  alkyl optionally having one or more oxygens substituted for carbon and optionally having one or more F atoms on the alkyl chain, 
         R f  is H, thiophene, furan, pyridine, benzene, thiazole, or C 1 -C 6  alkyl optionally having one or more oxygens substituted for carbon and optionally having one or more F atoms on the alkyl chain, 
         R is C 1 -C 6  alkyl and 
         X is halogen, bicarbonate (HCO 3   − ), carbonate, bisulfate (HSO 4   − ), bisulfite (HSO 3   − ), methane sulfonate (MeSO 3   − ), triethyl borohydride (Et 3 BH − ) or a C 1 -C 6  carboxylate. 
       
     
     
         11 . The polymer of  claim 10 , selected from a polymer containing N +  Ar, wherein N +  Ar is selected from the group consisting of 
       
         
           
           
               
               
           
         
         a polymer wherein R is buty; and 
         a polymer wherein R f  is H and R fa  is a bond. 
       
     
     
         12 . The polymer of  claim 1 , wherein X is Br or F. 
     
     
         13 . The polymer of  claim 1 , wherein X if F. 
     
     
         14 . A dopant for use with a conducting polymer comprising the polymer of  claim 1 . 
     
     
         15 . A composition comprising a conducting polymer and the dopant of  claim 14 . 
     
     
         16 . The composition of  claim 15 , comprising about 75% of the dopant. 
     
     
         17 . The composition of  claim 15 , wherein the conducting polymer has the structure 
       
         
           
           
               
               
           
         
         wherein Y 1  and Y 2  are independently —CH—, —S—, —O—, —N═, —NR 3 —; 
         Y 3  is O or NR 3 ; 
         R 3  is C 1 -C 12  alkyl optionally substituted with one or more F atoms; 
         R 4  is vinyl, acetylene, or a five or six membered aromatic ring optionally having one or two heteroatoms independently selected from N, S, and O; and 
         m is 0 or 1 such that, 
         when m is 0, Y 2  is —S—, —O—, or —NR 3 —, and   is a single bond, and 
         when m is 1, Y 2  is —CH or —N═, and   is a double bond. 
       
     
     
         18 . The composition of  claim 17 , wherein the conducting polymer is selected from the group consisting of 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         wherein, 
         R 1  and R 2  are independently H, a halogen, —CN, C 1 -C 12  alkyl or C 1 -C 12  alkoxy, 
         R 3  is C 1 -C 12  alkyl optionally substituted with one or more F atoms, 
         R 4  is a five or six membered aromatic ring optionally having one or two heteroatoms independently selected from N, S, and O, vinyl or acetylene. 
       
     
     
         19 . The composition of  claim 18 , wherein R 4  is selected from thiophene, furan, pyridine, benzene, thiazole, phenyl, or a derivative thereof. 
     
     
         20 . The composition of  claim 15 , wherein the conducting polymer is 
       
         
           
           
               
               
           
         
       
     
     
         21 . The composition of  claim 15 , wherein the dopant comprises 
       
         
           
           
               
               
           
         
       
     
     
         22 . A polymer having the structure 
       
         
           
           
               
               
           
         
         wherein NAr is a N-containing monocyclic or bicyclic aromatic ring having 1 or 2 N atoms and substituted with R b , wherein R b  is C 1 -C 12  alkyl, aralkyl, or C 1 -C 12  alkoxy, wherein any of the alkyl groups is optionally substituted with one or more F atoms; 
         Ar is a phenyl or naphthalene ring, optionally substituted with R c ′ or CO 2 Ph, wherein any of the phenyl or naphthalene rings is substituted with R c , wherein R c  is H, C 1 -C 12  alkyl optionally substituted with one or more F atoms, or C 1 -C 12  alkoxy optionally substituted with one or more F atoms; 
         R d  is H or Me; 
         the ratio of x:y is from about 99:1 to about 80:20. 
       
     
     
         23 . The polymer of  claim 22 , wherein NAr is selected from the group consisting of 
       
         
           
           
               
               
           
         
       
     
     
         24 . An electronic and/or electro-optic device comprising at least one polymer according to  claim 1 . 
     
     
         25 . A device, comprising:
 a first electrode;   a second electrode spaced apart from said first electrode; and   at least one of an electrically conducting or semiconductor material arranged between said first and second electrodes,   wherein at least one of said first and second electrodes comprises at least one polymer according to  claim 1 .   
     
     
         26 . The device according to  claim 25 , further comprising a third electrode arranged proximate said active material,
 wherein at least one of said at least one of an electrically conducting or semiconductor material is a semiconductor,   wherein said third electrode is a gate electrode,   wherein one of said first and second electrodes is a source electrode and the other of said first and second electrodes drain electrode such that said device is a transistor.